Dyestuffs of the phthalocyanine series



Patented Dec. 16, 1941 DYESTUFFS OF THE PHTHALOCTANINE r SERIES- Berthold Bienert, Levcrkusen-Wiesdorf, and Hermann 'Thielert, Cologne-Merheim, Germany,

assignors'to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application January 9, 1940, Serial No. 313,098. .In Germany December 30, 1938 4 Claims. (01. 260-3 14) The present invention relates to new watersoluble phthalocyanines which represent valuable substantive dyestuffs for vegetable fibers and are valuable starting materials for the preparation of color lakes. Our new products may be defined by the following formula:

X 7 v X V wherein in each of the nuclei one of the XS stands fora sulfonic acid group and the other X,

stands foran acylamino group and X indicates that the products contain a heavy metal incomplex combination. Such compounds -.of the.

character described are preferred as contain a heavy metal in complex combination and among The acylthose the copper phthalocyanines.

amino group may be of the aliphatic'or aromatic series, preferred substituents being the benzoylamino group and those derivatives thereof Ihav-. ing one or several of the .hydrogens of the hem zene nucleus replaced by alkoxy and/or halogen atoms. The new dyestuffs which correspond to the above formula exhibit an excellent aflinitytowards vegetable fibers, such as cotton and viscose orcuprammonium-silk and show. the most greenish shade which has been obtained up to the present within the class of water-soluble phthalocyanine dyestuffs. Moreover, the clearness of shade and the fastness properties of these compounds are such as cannot be found within any other class of dyestuffs, be it the azo, triphenylmethane or anthraquinone series.

We. are aware of the fact that acylamino phthalocyanines have been prepared prior to our present invention by sulfonating a tetraacetylamino copper phthalocyanine and reintroducing the acetyl radicals which have been split 01? dur- I ing the sulfonation process. We wish to .point out, however, that the prior known methods of after-sulfonation donotallow one to introduce into the phthalocyanine molecule more than two or at the most three sulfonic acid groups, where as our present compounds are characterized by their containing four sulfonic acid groups. Moreover, there is reason to assume that inthe case of an after-sulfonation the sulfonic acid group will never'enter the same position asin the case of our present compounds. At any rate, our present 'tetrasulfonic acid compounds are superior to the prior known products as tothe cleamess of ,shadesland. as to the fastnessto wards acids. j a

The new phthalocyanine dyestuffs can the prepared in various ways. For instance we can start from phthalic acids containing a sulfonic acid group in 4-position and an acylamino group in 5-position. Such starting materials can be converted into phthalocyanines by heating the same with urea. and metal salts, such as those of copper, nickel or cobalt without involving the erably performed in the presence of sulfonic acid,

oleum or chlorosulfonic acid. In accordance with still another process we are starting from 5-amino-4-sulfophthalic acids, convert the same into phthalocyanines in the manner described above and then subjecting the phthalocyanines thus obtained to the actionof an acylating agent. As a matterof fact, our new dyestufi s can also be employed as color lakes. For this purpose they are converted into insoluble salts, for instanceinto the calcium or barium salts, the resulting pigment dyestuffs being distinguished by an excellent cleames's and very good .fastness properties.

The invention is illustrated by the following examples, without being restricted thereto, the

partsbeing byweight: v

Y E'wa1fiple 1 3 the dyestuff formed being precipitated by the addition of common salt. ,By, redissolution from dilute soda solution and precipitation with common salt the dyestufi may be purified, if desired. It is readily soluble in water and dyes cotton clear green shades.

By heating the dyestuff with hydrochloric acid or sulfuric acid saponification takes place with the formation of :thesalts of the 5.5'.5'.' .5"'- tetraamino copperphthalocyanine 4.4'.4".4- tetrasulfonic acid, this product showing a bluishv coloration. This amino compound may be conmixture is added to 500 parts of ice water, the dyestuff precipitated being filtered off and washed neutral by means of common salt solution. Thereupon the dyestuff is dissolved in water with the addition of soda solution until the solution showsan alkaline reaction and is then precipitated by means of common salt. A dye- .stuif is obtained which dyes cotton green shades being more bluish than the dyeings according verted into new dyestuffs bYPEtIBfltm'Ght'. withg rlO to-Example-i.

other acylating agents as it is more fully de--i'- scribed in Example 5.

Example 2 5 If the monopotassium saltjofithe ,..5-acetyl;l

amino-4-su1fophthalic acid as described ample 1 is replaced by 136 parts of' the' monopo' tassium salt of the 5-benzoy-lamino 4-sulfo phthalic acid, a dyestuff is obtained being lreadilye. soluble in water which dyes cotton clear yellowish green shades;

Insteadcof copperchloride'zalsoiiothermetal salts may:be used,:fordnstanceinicke1e,1 cobalt; or iron: chloridexdyestufis of isimi-larproperties bGiIlgJObeIl tainedi'therebmrx,

The:51-acylamino-s-sulfophthaliezacids ing prepared according t th f ll i r c quation: I I

The monopotassium salts-of the acylaminosulfophthalio-lacids are 1colorlessicompoundswhichv are c readily-solublaior instancefinfwate A fnixtuieoffiOO parts of a 27% ammonia. solution, 0.5..part..of copper powdery. LO-part of. 7 copper. chloride and 50 parts :of rthensodium. salt:

corresponding...chloro compound. are heated to' 155-160'C. "in an autoclave while' stirring. .jor...

about 10 hours. I

The dyestuff sal-tprfecipitated is separatedwfro'mh the'ammon'ia solution, dissolved-inlwatersfiltered.

and reprecipitated from the filtrate by theaddition of common salt. A copper phthalocyanine- 4.4'..4"-.4' .(-tetrasulfonic. -acid is :obtained which inatheL-average containTA amino groupsi-n-the molecule .andvis especially suitable .for .being reel acted uponwithTacid chlorides,-such Jas. benzoyl-q chloride; I

' Example "4 6.652partsof thetaminosulfonicj acid according 7Q to-Example E3 are dissolved or suspended) in 40 51 parts 'of monohydrat'e and gradually 8.55 parts of-"acetio acidanhydride are added-drop-by drop at fi Q As soonastheshade of sa :test dissolved: int. wateriidoesxanot changeianynmore, the" 1.75

Example 5 6.65; parts of the amino sulfonic acid according toExampleB aredissolved (or suspended) in 40 parts-20f: chlorosulfonic acid and 8.85 parts of '"benzoyl'chloride are added drop by drop slowly at 20-30? C. As soon as the shade of a test dissolved; in water doesnot change any more, the

mixture is treated as described in Example 4, the

excess benzoic acid being removed by treatment with soda solution. The dyestuffobtained dyes cotton clear green shades which area trifle more bluish than'those accordingi to' Exampl 2. Examplafi If the behzoylchloride mentioned in Example-fi' is replaced by the corresponding: quantityof o-chlorobenzoylchloride, a dyestuff is obtained of a somewhat bluershade. 1

Example 7 If instead of ammonia as described in Example 3 methylamine or other primary amines are used, N-substitut'ed aminosulfonic 'acids are obtained which can beliconverted-by treatment with acid chlorideaccording to Example 5 (at somewhat higher temperatures) into'jacyl derivatives.

Example 8 24.3 parts of potassium 5-(2'.4'-dichlorobenzoylamino) l-sulfophthalate; 0.48 pa-rt of am:

tion;

A dyestuff is obtained being'solubl'e" in water whi'chdyes the vegetable 'fiber. clear green shades.

Example- 9 A mixture of' Parts. Ureair Potassium 5-(2'-chlorobenzoylamino) -4- sulfophthalate: 43,.75' Ammoniumzmolybdatel 0 33 Copper-":chlonden .4, 25:

is heated and worked up as described'inEXam ple 8. For-thepurpose of diluting the'melt'there may'beaddedfurther 33 parts of urea;

Whe'nworkingup accordingto'EXample-B a dyestufi' is obtained showing similar properties;-

Example .10.

If the': benzoylchloride': described in? Example 5 is replaced: by 4-ch1'orobenzoylchloride; also bluish-green dyestuffs'xarei obtainedawithita good affinity towards vegetable 'fibers';

Example 11 If the benzoylchloride of Example ,5. isfreplae d by 2a-.dichlorobenzoylchloride, a dyestuff is' obtained showing good properties similar to those of the dyestuff of Example 10.

Example 12 If the potassium 5-(2-chlorobenzoylamino) -4- sulfophthalate of Example 9 is replaced by the corresponding quantity of potassium 5-(2- bromo-benzoylamino)-4-su1fophthalate, a dyestufi is obtained which dyes cotton grayishgreen shades.

Example 13 In the same way as described in Example 9 a copper phthalocyanine can be obtained from pctassium 5 (3 chlorobenzoylamino) 4 sulfophthalate. The dyestuff is difficultly soluble in Water.

Example 14 In the same Way as described in Example 9 a copper phthalocyanine can be obtained from potassium 5 (4' chlorobenzoylamino) 4 sulfophthalate. The dyestuif is still more difficultly soluble than that obtained according to Example 13.

Example 15 According to Example 8 from potassium 5-(2.5' dichlorobenzoylamino) -4-sulfophthalate a dyestufi is obtained being readily soluble in water which, for instance, dyes cotton clear green shades.

Example 16 Into a melt of 8.66 parts of urea there is added while stirring a mixture of Urea, parts Potassium 5-(2-methoxybenzoylamino) 4-sulfophthalate parts 17.32 Crystallized copper chloride grams 1.70 Ammonium molybdate do 0. 48

Example 17 If the starting material described in Example 16 is replaced by the corresponding meta-methoxybenzoylamino compound, dyestuffs are obtained of similar properties.

Example 18 If in Example 1'? instead of the meta-methoxybenzoylamino compound the para-methoxybenzoylamino compound is used, a dyestuif is obtained showing similar properties.

Example 19 To a melt of 8.2 parts of urea there is added while stirring at ISO-165 C. a mixture of Parts 32. 8

Urea

Potassium 5- (2 -chloro-5 -methoxybenzoylamino)-4-sulfophthalate 32.8

Crystallized copper chloride 3.4

Ammonium molybdate The melt kept at 16D+165 C. for about 4 hours, further 8.2 partsef ureabeing added thereto:

-- Adyestufi is. obtained being readily soluble in water, which dyes the vegetable fiber bluishe greenshades, which are still more bluish than those? of the dyestufi obtained according to Exam-ple 16. f

Example 20 If according to Example 19 the potassium 5 (2-chloro-6-methoxybenzoylamino) -4-sulfophthalate is used, a dyestufi' is obtained being very readily soluble in water and showing a slight aflinity to cotton.

Example 21 Into a melt of 4.6 parts of urea there is added while stirring at 165 C. a mixture of Parts. Urea 18.4 Potassium 5 (3'-acetylaminobenzoylamino) -4-sulfophthalate 18.4 crystallized copper chloride 1.7 Ammonium molybdate 0.56

The melt is still heated at 160-165 for about 4-5 hours, further 4.6 parts of urea being added thereto. usual manner the resulting dyestufi being diflicultly soluble and less suitable for the dyeing of vegetable fibers but showing an excellent fastness to light if employed as lake dyestuff.

Example 22 If the potassium 5-(3'-acetylaminobenzoylamino) -4-sulfophthalate according to the preceding example is replaced by potassium 5-(4'-acetylaminobenzoylamino) -4-sulfophthalate a dyestuff is obtained which is less suitable for the dyeing of vegetable fibers but shows an equally excellent fastness to light if employed as lake dyestuff.

Example 23 4.03 parts of urea are molten; thereupon a mixture of Urea 16. 12 Potassium 5-benzoylamino-4-sulfophthalate 16. 12 Crystallized nickel chloride 2. 38 Ammonium molybdate 0. 403

is added while stirring at 160-165" C. While adding from time to time 16.12 parts of urea the melt is kept for further 4 hours at ISO- C. and the working up is performed in the usual manner.

The dyestuff dyes cotton somewhat duller and more bluish shades than the corresponding copper dyestuff.

We claim:

1.- Heavy metal complexes of the products of the following formula:

wherein in each of. the nuclei one of the Xs The working up is performed in the- Parts stands for a sulionic acid group and the other X the acylamino group is a halogenbenzoylamino stands for an acylamino group and Y indicates group.

that the products contain a heavy metal in com- 4. The products as claimed in claim 1 wherein plex combination. the acylamino group is an alkoxybenzoylamino 2. The products as claimed in claim 1 wherein 5 group.

the acylamino group is a benzoylamino'group. BERTHOLD BIENERT.

3. The products as claimed in claim 1, wherein HERMANN THIELERT. 

